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Phenylarsonic acid compounds, which were widely used in poultry and swine production, are often introduced to agricultural soils with animal wastes. Fenton coagulation process is thought as an efficient method to remove them. However, the substituted amino group could apparently influence the removal efficiency in Fenton coagulation process. Herein, we investigated the optimal conditions to treat typical organoarsenic contaminants (p-arsanilic acid (p-ASA) and phenylarsonic acid (PAA)) in aqueous solution based on Fenton coagulation process for oxidizing them and capturing the released inorganic arsenic, and elucidated the influence mechanism of substituted amino group on removal. Results showed that the pH value and the dosage of H2O2 and Fe2+ significantly influenced the performance of the oxidation and coagulation processes. The optimal conditions for removing 20 mg L-1-As in this research were 40mg L-1 Fe2+ and 60mg L-1 H2O2 (the mass ratio of Fe2+/H2O2 = 1.5), initial solution pH of 3.0, and final solution pH of 5.0 adjusting after 30-min Fenton oxidation reaction. Meanwhile, the substituted amino group made p-ASA much more easily be attacked by ·OH than PAA and supply one more binding sites for forming complexes with Fe3+ hydrolysates, resulting in 36% higher oxidation rate and 7% better coagulation performance at the optimal conditions.

Hypothesis Aromatic organoarsenicals are heavily used as poultry feed additives, and the application of manure containing these compounds could release toxic inorganic arsenic into the environment. Bimetal ferrites are recognized as promising sorbents in removal of organoarsenicals with formation of Fe O As complexes, and their high saturation magnetization also allows easy sorbent separation. Experiments Herein, a flower-like CoFe2O4 sorbent was synthesized through an environmental-friendly process. Findings The flower-like CoFe2O4 particles have abundant mesopores and a large specific surface area of 48.4 m2/g. At an equilibrium concentration of 80 μmol/L, the sorption capacities towards p-arsanilic acid (p-ASA), roxarsone (ROX), 4-hydroxyphenylarsonic acid (4-HPAA), 2-aminophenylarsonic acid (2-APAA), phenylarsonic acid (PAA), and 2-nitrophenylarsonic acid (2-NPAA) were 38.1, 45.7, 38.7, 39.3, 33.0, and 32.8 mg/g, respectively. Langmuir model and pseudo-second-order kinetics could well fit the sorption isotherms and rates. The sorption performance was better under acidic conditions due to enhanced electrostatic attraction. Humic acid (HA) and PO43− inhibited the sorption through competing for sorption sites, while Fe3+ promoted sorption due to formation of additional Fe O As complexes on sorbent surface. The experimental observations, spectroscopic insights, and density functional theory (DFT) calculations consistently indicate that the sorption of aromatic organoarsenicals on the flower-like CoFe2O4 particles occurs mainly through formation of inner-sphere complexes. The flower-like CoFe2O4 could be regenerated and reused over multiple cycles. The high sorption capacities, together with its magnetic property, make the flower-like CoFe2O4 an attractive sorbent for removing aromatic organoarsenicals from wastewater.

Phenylarsonic acid compounds could be oxidized by manganese oxides in surface soils, resulting in quick release of inorganic arsenic. This study investigated the structure–reactivity relationships ...

The crystal structure and supramolecular architectures of Schiff bases derived from the o-arsanilic acid, (E)-(2-(4-hydroxybenzylidene)aminophenyl)arsonic acid(I); (E)-(2-(4-methoxybenzylidene)aminophenyl)arsonic acid (II) and (E)-(2-(3-cyanobenzylidene)aminophenyl)arsonic acid (III) are reported. The intermolecular interactions, supramolecular architectures, and molecular conformations are compared with the (E)-(2-(2-hydroxybenzylidene)aminophenyl)arsonic acid(IV) to evaluate how different substituents influence the crystal packing. In the solid state, the O−H⋯O hydrogen bonding interaction predominantly stabilizes the crystal structures of I-IV. Further, the weak intermolecular C−H⋯O, C−H⋯N, C−H···π, π···π, and H⋯H contacts form a self-assembled motif. Various intermolecular interactions exist in I-IV and their energies are quantified using PIXEL, DFT and QTAIM analysis. The variant and invariant arsanilic acid dimers are observed in I-IV. The distribution of electrostatic potential on the molecular surface is found to be asymmetric nature in I-IV. The relative contributions of various intermolecular contacts in the I-III and the closely related analog (IV) are quantified by using Hirshfeld surface analysis and the decomposed 2D fingerprint plots. The total lattice energy of compound III is higher than the other compounds. It is due to the cyano substitution in III because the −CN group participates in the C−H⋯N interactions which favored very compact packing. Also, the contribution of intermolecular H⋯H, O⋯H/H⋯O, and C⋯H/H⋯C contacts are drastically reduced in III when compared with other compounds, this reduction is due to more contribution of H⋯N contacts in the crystal structure.

Organic arsenics have been frequently detected in natural environments and regarded as a group of emerging contaminants. Elucidating the migration of organic arsenics requires a deep understanding of intrinsic adsorption mechanisms of organic arsenics on iron-bearing minerals, which are seldom investigated. In this study, we investigated the facet-dependent adsorption behavior of phenylarsonic acid (PhAs) on hematite nanocrystals with open circuit potential (OCP) analysis, batch adsorption experiments, adsorption isotherm curves, synchrotron-based As K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, and density functional theory (DFT) calculations. We found that organic arsenics adsorbed on two facets (e.g. {001} and {012}) of hematite through the same non-protonated inner-sphere coordination but in different molecular configurations. Surface complexation models were set up to analyze the preferred coordination geometries dependent on the facets, and the {012} facet was found to favor the PhAs adsorption more than the {001} facet. These findings clarified the dependence of organic arsenic adsorption on the hematite facets, and shed light on the environmental effects of hematite on the migration of PhAs.

Adsorption and desorption of p-arsanilic acid (p-ASA) and roxarsone (ROX) on six soil minerals, including hematite (α-Fe2O3), goethite (α-FeOOH), ferrihydrite (Fe(OH)3), aluminum oxide (α-Al2O3), manganese oxide (γ-MnO2), and kaolinite, were studied, and the impact of solution matrices on their adsorption was systematically evaluated. Adsorption of p-ASA/ROX on the metal (hydro)oxide and clay minerals occurred quickly (mostly within 2 h), and could be well described by the pseudo second-order kinetic model. The apparent maximum adsorption capacities of α-Fe2O3, α-FeOOH, Fe(OH)3, α-Al2O3, γ-MnO2, and kaolinite (at an initial pH of 7.0) for p-ASA were 1.7, 0.9, 2.5, 0.08, 1.1, and 0.02 μmol/m2, while those for ROX were 1.6, 0.7, 2.4, 0.1, 0.5, and 0.05 μmol/m2, respectively. Besides adsorbing p-ASA/ROX, γ-MnO2 also caused their oxidation. Experimental results suggest that formation of inner-sphere complexes through the arsonic acid group is the primary mechanism for adsorption of p-ASA/ROX on iron (hydro)oxides and γ-MnO2, while outer-sphere complexation plays a critical role in their adsorption on α-Al2O3 and kaolinite. Adsorption of p-ASA/ROX on the metal (hydro)oxide and clay minerals was affected by solution pH, co-existing metal ions (Ca2+, Mg2+, Al3+, Cu2+, Fe3+, and Zn2+), oxyanions (H2PO4−, HCO3−, and SO42−), and humic acid. The solid-to-liquid partition coefficients of p-ASA during the desorption from α-Fe2O3, α-FeOOH, Fe(OH)3, α-Al2O3, γ-MnO2, and kaolinite were 0.47, 2.69, 4.38, 0.03, 30.4, and 0.1 L/g, while those of ROX were 0.28, 1.68, 3.48, 0.02, 4.0, and 0.02 L/g, respectively. Agricultural soils with lower contents of organic carbon exhibited higher adsorption capacities towards p-ASA/ROX, which indicates that soil minerals play a key role in the adsorption of phenylarsonic acid compounds while organic matter could have strong inhibitory effect. These findings could help better understand and predict the transport and fate of p-ASA/ROX in surface soils with low contents of organic matter.

The interconversion of CO2 and HCO3&minus, is catalyzed by a superfamily of metalloenzymes, known as carbonic anhydrases (CAs, EC 4.2.1.1), which maintain the equilibrium between dissolved inorganic CO2 and HCO3&minus, In the genome of Escherichia coli, a Gram-negative bacterium typically colonizing the lower intestine of warm-blooded organisms, the cyn operon gene includes the CynT gene, encoding for a &beta, CA, and CynS gene, encoding for the cyanase. CynT (&beta, CA) prevents the depletion of the cellular bicarbonate, which is further used in the reaction catalyzed by cyanase. A second &beta, CA (CynT2 or Can or yadF), as well as a &gamma, and &iota, CAs were also identified in the E. coli genome. CynT2 is essential for bacterial growth at atmospheric CO2 concentration. Here, we characterized the kinetic properties and the anion inhibition profiles of recombinant CynT2. The enzyme showed a good activity for the physiological CO2 hydratase reaction with the following parameters: kcat = 5.3 &times, 105 s&minus, 1 and kcat/KM = of 4.1 &times, 107 M&minus, 1 s&minus, 1. Sulfamide, sulfamate, phenylboronic acid, phenylarsonic acid, and diethyldithiocarbamate were the most effective CynT2 inhibitors (KI = 2.5 to 84 &micro, M). The anions allowed for a detailed understanding of the interaction of inhibitors with the amino acid residues surrounding the catalytic pocket of the enzyme and may be used as leads for the design of more efficient and specific inhibitors.

To quantify aromatic arsines in the environment, such as World War I era chemical warfare agents and degradation products of arsenicals used in agriculture, a sensitive, selective, and direct method is needed. We describe the development and optimization of a method for the measurement of trace levels of triphenylarsine used as a model aromatic arsenic compound. Triphenylarsine was determined at low µg/g levels in sand, soil, and lake sediment by thermal desorption before gas–liquid chromatography (GC) with mass spectrometric and pulsed flame photometric detection. The dithiol derivative of phenylarsonic acid was used as an internal standard, thereby significantly improving the precision of the method. The desorption conditions were studied and found to be optimal at 350°C for 15 min. Significant improvement in precision was realized by preparing the solid samples as slurries in acetone and by inserting a small (∼100 mg) quartz wool plug into the sample vial. The method was applied to determine tr...

An anion inhibition study of the β-class carbonic anhydrase, AgaCA, from the malaria mosquito Anopheles gambiae is reported. A series of simple as well as complex inorganic anions, and small molecules known to interact with CAs were included in the study. Bromide, iodide, bisulphite, perchlorate, perrhenate, perruthenate, and peroxydisulphate were ineffective AgaCA inhibitors, with KIs > 200 mM. Fluoride, chloride, cyanate, thiocyanate, cyanide, bicarbonate, carbonate, nitrite, nitrate, sulphate, stannate, selenate, tellurate, diphosphate, divanadate, tetraborate, selenocyanide, and trithiocarbonate showed KIs in the range of 1.80–9.46 mM, whereas N,N-diethyldithiocarbamate was a submillimolar AgaCA inhibitor (KI of 0.65 mM). The most effective AgaCA inhibitors were sulphamide, sulphamic acid, phenylboronic acid and phenylarsonic acid, with inhibition constants in the range of 21–84 µM. The control of insect vectors responsible of the transmission of many protozoan diseases is rather difficult nowadays, and finding agents which can interfere with these processes, as the enzyme inhibitors investigated here, may arrest the spread of these diseases worldwide.

International audience; Infrared spectroscopy Thermal behavior a b s t r a c t A new semi-organic hydrogen bonding complex salt of 2-ammonium phenylarsonic acid and nitric acid has been synthesized, thus successfully growing good quality single crystals by means of slow solvent evaporation technique at ambient temperature. The 1 H and 13 C NMR spectra were recorded to establish the molecular structure. The conducted single crystal XRD analysis has shown that the title salt is crystalized in orthorhombic crystal system with centrosymmetric Pbcm space group. The structure consists of infinite parallel two-dimensional planes built of (C 6 H 6 NH 3 AsO 3) þ organic cation and NO À 3 inorganic anions connected by hydrogen bonds and p-p interactions giving birth a three-dimensional network. The performed TG/DSC thermal analysis has established the thermal stability of the crystal. The optimized structural parameters and vibrational frequencies (the experimental and theoretical vibrational frequencies) were assigned and compared by the Density Functional Theory (DFT) using the Gaussian method (DFT/B3LYP). Good consistency results were found between the calculated and the experimental crystal structure and FT-IR spectra.

Organic arsenic acids (OAAs) are regarded as water pollutants because of their toxicity and considerable solubility in water. Adsorption of OAAs such as phenylarsonic acid (PAA) and p-arsanilic acid (ASA) from water was investigated over functionalized (with OH groups) metal-organic framework (MOF, MIL-101), as well as over pristine MIL-101 and commercial activated carbon. The highly porous MIL-101 bearing three hydroxyl groups (MIL-101(OH)3) exhibited remarkable PAA and ASA adsorption capacities. Based on the effects of pH on PAA and ASA adsorption, hydrogen bonding was suggested as a plausible mechanism of OAA adsorption. Importantly, OAAs and MIL-101(OH)3 can be viewed as hydrogen-bond acceptors and donors, respectively. Moreover, MIL-101(OH)3 could be regenerated by acidic ethanol treatment, being a promising adsorbent for the removal of PAA and ASA from water.

Aromatic organoarsenic compounds tend to transform into more mobile toxic inorganic arsenic via several processes, and can inadvertently spread toxic inorganic arsenic through the environment to water sources. To gain insight into the transformation mechanisms, we herein investigated how the process of para arsanilic acid (p-ASA) transformation works in detail on the surface of adsorbents by comparing it with phenylarsonic acid (PA) and aniline, which have similar chemical structures. In contrast to the values of 0.23 mmol g−1 and 0.68 mmol g−1 for PA and aniline, the maximum adsorption capacity was determined to be 0.40 mmol g−1 for p-ASA at pH 4.0. The results of FTIR and XPS spectra supported the presence of a protonated amine, resulting in a suitable condition for the oxidation of p-ASA. Based on the combined results of UV-spectra and UPLC-Q-TOF-MS, we confirmed that the adsorbed p-ASA was first oxidized through the transfer of one electron from p-ASA on MnO2 surface to form a radical intermediate, which through further hydrolysis and coupling led to formation of benzoquinone and azophenylarsonic acid, which was identified as a major intermediate. After that, p-ASA radical intermediate was cleaved to form arsenite (III), and then further oxidized into arsenate (V) with the release of manganese (Mn) into solution, indicating a heterogeneous oxidation process.

We report the cloning, purification and characterization of Bps beta CA, a beta-class carbonic anhydrase (CA, EC 4.2.1.1) from the pathogenic bacterium Burkholderia pseudomallei, the etiological agent of melioidosis, and compare its activity and inhibition with those of the gamma-CA from the same organism, Bps gamma CA, recently investigated by our groups. Bps beta CA showed a significant catalytic activity for the physiologic, CO2 hydration reaction, with the following kinetic parameters, k(cat) of 1.6 x 10(5) s(-1) and k(cat)/K-m of 3.4 x 10(7) M-1 x s(-1). The inhibition of Bps beta CA with a group of anions and small molecules was also investigated. The best inhibitors were sulfamide, sulfamic acid and phenylarsonic acid, which showed K(I)s in the range of 83-92 mu M, whereas phenylboronic acid, fluoride, cyanide, azide, bisulfite, tetraborate, perrhenate, perruthenate, peroxydisulfate, perchlorate, tetrafluoroborate, fluorosulfonate and hexafluorophosphate showed K(I)s > 100 mM. Other inhibitors of this new enzyme were bicarbonate, trithiocarbonate, some complex inorganic anions and N,N-diethyldithiocarbamate, which had inhibition constants of 0.32-8.6 mM. As little is known of the life cycle and virulence of this bacterium, this type of study may bring information of interest for the development of novel strategies to fight bacterial infection and drug resistance to commonly used antibiotics. (C) 2017 Elsevier Ltd. All rights reserved.

Roxarsone (ROX) is an emerging arsenic pollutant due to its potential degradation into highly toxic inorganic arsenic species in the environment. Adsorbents which can capture ROX with both high capacity and affinity are urgently needed. Herein, a nanocomposite of nano-Fe3O4 and three-dimensional graphene (Fe3O4@RGO) was designed, aiming to simultaneously attract arsenate and benzene groups in ROX. Characterization of the nanocomposite revealed that Fe3O4 nanoparticles (20–50 nm) with exposed (400) planes were highly dispersed on the graphene support. Adsorption experiments showed that Fe3O4@RGO had higher adsorption capacity, affinity, and adsorption rate towards ROX than pristine materials and efficiently removed ROX from both simulated natural and waste waters. The adsorption mechanism was confirmed as a synergetic interaction of As–Fe coordination, hydrogen bonding and π–π interaction. X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS) results suggested that the As–Fe complexes and hydrogen bonds between Fe3O4@RGO and ROX were stronger than those in pristine nano-Fe3O4, due to the greater number of surface hydroxyls and shorter As–Fe atomic distance in Fe3O4@RGO. The π–π interaction between ROX and the graphene part in Fe3O4@RGO was also enhanced. This study provided a novel idea for designing materials to remove pollutants with both inorganic and organic moieties, such as phenylarsonic acid compounds, from water.

Large quantities of chemical warfare agents (CWAs), such as phenylarsenic chemicals, were disposed by sea-dumping after World War II. Nowadays, the release of these toxic chemicals from munitions poses a potential threat to living organisms. This study investigates the fate of these chemicals in fish by exposing selected CWA-related phenylarsenic chemicals and their oxidation products to cod (Gadus morhua) liver S9 fraction in vitro. Clark I (DA), Adamsite (DM) and their corresponding oxidation products as well as triphenylarsine oxide (TPA[ox]) and phenylarsonic acid (PDCA[ox]) were used as chemicals in in vitro experiments. Glutathione (GSH) conjugates of DA, DM and PDCA-related chemicals were found to be the most dominant metabolites, and methylated metabolites were detected as well, suggesting that these compounds are metabolised in the presence of cod liver enzymes. TPA[ox] was the only compound tested that did not form a GSH conjugate or methylated metabolite, indicating a different biotransformation pathway for this compound. Furthermore, hydroxylated metabolites were detected for each tested chemical. Due to their reactive nature, GSH conjugates may be difficult to detect in fish samples from CWA dumpsites. In contrast, both methylated and hydroxylated metabolites of phenylarsenic chemicals are promising target chemicals for the detection of CWA-related contamination in fish.

We report the cloning and catalytic activity of a β-carbonic anhydrase (CA, EC 4.2.1.1), isolated from the pathogenic protozoan Entamoeba histolytica, EhiCA. This enzyme has a high catalytic activity for the physiologic CO2 hydration reaction, with a kcat of 6.7 × 105 s−1 and a kcat/Km of 8.9 × 107 M−1 × s−1. An anion inhibition study of EhiCA with inorganic/organic anions and small molecules revealed that fluoride, chloride, cyanide, azide, pyrodiphosphate, perchlorate, tetrafluoroborate and sulfamic acid did not inhibit the enzyme activity, whereas pseudohalides (cyanate and thiocyanate), bicarbonate, nitrate, nitrite, diethyldithiocarbamate, and many complex inorganic anions showed inhibition in the millimolar range (KIs of 0.51–8.4 mM). The best EhiCA inhibitors were fluorosulfonate, sulfamide, phenylboronic acid and phenylarsonic acid (KIs in the range of 28–86 μM). Since β-CAs are not present in vertebrates, the present study may be useful for detecting lead compounds for the design of effective enzyme inhibitors, with potential to develop anti-infectives with alternative mechanisms of action.

The protozoan pathogen Trichomonas vaginalis encodes two carbonic anhydrases (CAs, EC 4.2.1.1) belonging to the β-class. One of these enzymes, T. vaginalis carbonic anhydrase 1 (TvaCA1), was recently cloned and characterized by our group, and its X-ray crystal structure reported. No inhibitors of this enzyme were reported up until now. Here we investigated the inhibition of TvaCA1 with inorganic anions and small molecules and observed that thiocyanate, cyanide, selenite, selenocyanate and divanadate are sub-millimolar inhibitors, whereas sulfamide, sulfate, phenylboronic acid and phenylarsonic acid are micromolar inhibitors. Finding effective TvaCA1 inhibitors may be useful for developing new antiprotozoan drugs. acceptedVersion

Being highly water-soluble, phenylarsonic feed additives discharged in animal wastes can easily accumulate in surface water bodies. The photodegradation mechanism, kinetics, and pathways of p-arsanilic acid (p-ASA), 4-hydrophenylarsonic acid (4-HPAA), and phenylarsonic acid (PAA) in water under simulated and natural sunlight irradiation were investigated. The -AsO(OH)2 group was cleaved from the aromatic ring during photodegradation, and p-benzoquinone and p-hydroquinone were formed as the major organic degradation intermediates. Experimental results did not indicate any significant direct photolysis of the phenylarsonic compounds under simulated and natural sunlight irradiation, but consistently showed that they sensitized the formation of singlet oxygen, which was responsible for their photodegradation and oxidation of the As(III) released. A simple (1)O2-based "heterogeneous" model was developed, which could well describe the kinetics of (1)O2 formation and phenylarsonic compound photodegradation under various conditions. Indirect photolysis caused by inorganic ions commonly present in natural waters was negligible, while natural organic matter could significantly inhibit their photodegradation. The half-lives of p-ASA, 4-HPAA, and PAA photodegradation under simulated sunlight irradiation (765 W m(-2), 25 °C) were 11.82 ± 0.19, 20.06 ± 0.10, and 135 ± 6.0 min, respectively, while their degradation rates under natural sunlight in the Pearl River Delta of southern China were 5 times slower due to lower irradiation intensity and water temperatures (19-23 °C).

We have cloned, purified and characterized the gamma-carbonic anhydrase (CA, EC 4.2.1.1) present in the genome of the Antarctic bacterium Colwellia psychrerythraea, which is an obligate psychrophile. The enzyme shows a significant catalytic activity for the physiologic reaction of CO2 hydration to bicarbonate and protons, with the following kinetic parameters: k(cat) of 6.0 x 10(5) s(-1) and a k(cat)/K-m of 4.7 x 10(6) M-1 x s(-1). This activitywas inhibited by the sulfonamide CA inhibitor (CAI) acetazolamide, with a K-I of 502 nM. A range of anions was also investigated for their inhibitory action against the new enzyme CpsCA. Perchlorate, tetrafluoroborate, fluoride and bromide were not inhibitory, whereas cyanate, thiocyanate, cyanide, hydrogensulfide, carbonate and bicarbonate showed K(I)s in the range of 1.4-4.4 mM. Diethyldithiocarbamate was a better inhibitor (K-I of 0.58 mM) whereas sulfamide, sulfamate, phenylboronic acid and phenylarsonic acid were the most effective inhibitors detected, with K(I)s ranging between 8 and 38 mu M. The present study may shed some more light regarding the role that gamma-CAs play in the life cycle of psychrophilic bacteria as the Antarctic one investigated here. (c) 2016 Elsevier Ltd. All rights reserved.

A simple and sensitive derivatization method using toluene-3,4-dithiol as a derivatization reagent for the simultaneous analysis of seven arsenic compounds (roxarsone, nitarsone, p-arsanilic acid, o-arsanilic acid, phenylarsonic acid, phenylarsine oxide, and mono-methylarsonic acid) in chicken muscle was developed and validated by ultra-performance liquid chromatography coupled with ultraviolet detection (UPLC-UV). The structure of the derivatized arsenic compounds was confirmed by liquid chromatography-ion trap mass spectrometry or gas chromatography-mass spectrometry. Optimization of the derivatization reaction conditions was carried out by investigating the influence of reagent concentration, buffer or additive acids, temperature, and time. The optimized conditions were a derivatization reagent concentration of 20mg/mL with 0.05mol/L HCl as an additive acid at 60°C for 15min. In this study, baseline separation of arsenic compounds could be achieved within 13min, except for phenylarsonic acid and phenylarsine oxide whose derivatized products are equal. The developed method was successfully validated and applied to 12 chicken muscle samples from Korean districts and other countries.

Herein, an amino-modified electrospun nanofibrous cellulose membrane (CA-PVAm) was prepared and employed to adsorb the typical organoarsenic contaminants (roxarsone (ROX), p-arsanilic acid (p-ASA), and phenylarsonic acid (PAA)). The SEM, FT-IR, and XPS results showed that the CA-PVAm composed of abundant nanofibres and owned ample functional groups such as NH2, OH, and C O groups. The batch experiments demonstrated that the CA-PVAm exhibited excellent adsorption performance on ROX (186.22 mg g−1), p-ASA (69.15 mg g−1), and PAA (62.77 mg g−1), which were 15.98, 6.83, and 6.25 folds larger than those of the pristine CA. In addition, the adsorption process of ROX, p-ASA, and PAA on CA-PVAm accorded with the Langmuir model and obeyed the pseudo-second-order model with intraparticle diffusion. Meanwhile, the adsorption of ROX and PAA was endothermic process, but the exothermic process was observed during the p-ASA adsorption. Furthermore, the main adsorption mechanisms involved electrostatic interactions and hydrogen-bonding interactions. The formed stable six-membered structure between NH2 and NO2 groups could significantly enhance the hydrogen-bonding interactions between CA-PVAm and ROX molecule, resulting in evident improvement in ROX adsorption. Importantly, the CA-PVAm displayed outstanding reusability (4 cycles) and rapid desorption rate. This study probably provides an important theoretical and experimental basis for the remediation of the emerging organic pollutants.

CruCA4 is a secreted isoform of the α-carbonic anhydrase (CA, EC 4.2.1.1) family, which has been identified in the octocoral Corallium rubrum. This enzyme is involved in the calcification process leading to the formation of the coral calcium carbonate skeleton. We report here experiments performed on the recombinant CruCA4 with the technique of protonography that can be used to detect in a simple way the enzyme activity. We have also investigated the inhibition profile of CruCA4 with one major class of CA inhibitors, the inorganic anions. A range of weak and moderate inhibitors have been identified having KI in the range of 1-100 mM, among which the halides, pseudohalides, bicarbonate, sulfate, nitrate, nitrite, and many complex inorganic anions. Stronger inhibitors were sulfamide, sulfamate, phenylboronic acid, phenylarsonic acid, and diethylditiocarbamate, which showed a better affinity for this enzyme, with KI in the range of 75 μM-0.60 mM. All these anions/small molecules probably coordinate to the Zn(II) ion within the CA active site as enzyme inhibition mechanism.

Carbonic anhydrases (CAs) are metallo-enzymes that catalyze the reversible hydration of carbon dioxide into bicarbonate and a proton. The β-class CAs (β-CAs) are expressed in prokaryotes, fungi, plants, and more recently have been isolated in some animals. The β-CA class is divided into two subclasses, termed type I and II, defined by pH catalytic activity profile and active site structural configuration. Type I β-CAs display catalytic activity over a broad pH range (6.5-9.0) with the active site zinc tetrahedrally coordinated by three amino acids and a hydroxide/water. In contrast, type II β-CAs are catalytically active only at a pH 8 and higher where they adopt a functional active site configuration like that of type I. However, below pH 8 they are conformationally self-inactivated by the addition of a fourth amino acid coordinating the zinc and thereby displacing the zinc bound solvent. We have determined the structure of psCA3, a type II β-CA, isolated from Pseudomonas aeruginosa (P. aeruginosa) PAO1 at pH 8.3, in its open active state to a resolution of 1.9 Å. The active site zinc is coordinated by Cys42, His98, Cys101 and a water/hydroxide molecule. P. aeruginosa is a multi-drug resistant bacterium and displays intrinsic resistance to most of the currently used antibiotics; therefore, there is a need for new antibacterial targets. Kinetic data confirm that psCA3 belongs to the type II subclass and that sulfamide, sulfamic acid, phenylboronic acid and phenylarsonic acid are micromolar inhibitors. In vivo studies identified that among six tested inhibitors representing sulfonamides, inorganic anions, and small molecules, acetazolamide has the most significant dose-dependent inhibitory effect on P. aeruginosa growth.

A new ?-class carbonic anhydrase (CA, EC 4.2.1.1) was cloned, purified and characterized from the Antarctic bacterium Pseudoalteromonas haloplanktis, PhaCA?. The enzyme has a medium-low catalytic activity for the physiologic reaction of CO2 hydration to bicarbonate and protons, with a kcat of 1.4 × 105 s-1 and a kcat/Km of 1.9 × 106 M-1 s-1. An anion inhibition study of PhaCA? with inorganic anions and small molecule inhibitors is also reported. Many anions present in sea water, such as chloride, fluoride, sulfate, iodide, but also others such as azide, perchlorate and tetrafluoroborate did not inhibit this enzyme. Pseudohalides such as cyanate, thiocyanate, cyanide, selenocyanide, and also bicarbonate, nitrate, nitrite and many complex inorganic anions showed inhibition in the millimolar range (KI in the range of 1.7-9.3 mM). The best PhaCA? inhibitors detected in this study were diethyldithiocarbamate (KI of 0.96 mM) as well as sulfamide, sulfamate, phenylboronic acid and phenylarsonic acid (KI in the range of 82-91 ?M). Since ?-CAs are poorly understood at this moment, being present in carboxysomes and thus involved in photosynthesis, this study may be relevant for a better understanding of these processes in Antarctic bacteria/cyanobacteria.

The structure of the Schiff base (E)-2-[(2-hydroxybenzylidene)amino]phenylarsonic [(E)-HBAPhAA], synthesized from salicylaldehyde and o-aminophenylarsonic acid in the presence of HCl, was characterized by FTIR, 1H NMR, EI-MS, UV–Vis spectroscopy, and X-ray crystallography. The crystal belonged to the monoclinic space group P21/c. Two molecules formed a dimer via intermolecular interactions due to the attachment of H atoms to O1, O3 and O4 with O H bond distances within reasonable ranges, ca. 0.84(3) A. The structure also showed two intramolecular interactions of 2.634(2) and 3.053(2) A for N H⋯O hydrogen bonds, which caused the structures to be almost planar. We performed a theoretical analysis using DFT theory at B3LYP/6-31+G(d,p) level to determine the stability of the E and Z conformers. The geometry analysis of the E- and Z-isomers revealed an interconversion energy barrier between E/Z isomers of 22.72 kcal mol−1. We also theoretically analyzed the keto form of the E-isomer and observed a small energy barrier for the tautomerization of 6.17 kcal mol−1.

The carbonic anhydrase (CA, EC 4.2.1.1) superfamily of metalloenzymes catalyzes the hydration of carbon dioxide to bicarbonate and protons. The catalytically active form of these enzymes incorporates a metal hydroxide derivative, the formation of which is the rate-determining step of catalytic reaction, being affected by the transfer of a proton from a metal-coordinated water molecule to the environment. Here, we report the cloning, expression, and purification of a particular CA, i.e., nacrein-like protein encoded in the genome of the Pacific oyster Magallana gigas (previously known as Crassostrea gigas). Furthermore, the amino acid sequence, kinetic constants, and anion inhibition profile of the recombinant enzyme were investigated for the first time. The new protein, CgiNAP2X1, is highly effective as catalyst for the CO₂ hydration reaction, based on the measured kinetic parameters, i.e., kcat = 1.0 × 10⁶ s(-1) and kcat/KM = 1.2 × 10⁸ M(-1)·s(-1). CgiNAP2X1 has a putative signal peptide, which probably allows an extracellular localization of the protein. The inhibition data demonstrated that the best anion inhibitors of CgiNAP2X1 were diethyldithiocarbamate, sulfamide, sulfamate, phenylboronic acid and phenylarsonic acid, which showed a micromolar affinity for this enzyme, with KIs in the range of 76-87 μM. These studies may add new information on the physiological role of the molluskan CAs in the biocalcification processes.

The paper presents results of the studies photodegradation, photooxidation, and oxidation of phenylarsonic acid (PAA) in aquatic solution. The water solutions, which consist of 2.7 g dm(-3) phenylarsonic acid, were subjected to advance oxidation process (AOP) in UV, UV/H2O2, UV/O3, H2O2, and O3 systems under two pH conditions. Kinetic rate constants and half-life of phenylarsonic acid decomposition reaction are presented. The results from the study indicate that at pH 2 and 7, PAA degradation processes takes place in accordance with the pseudo first order kinetic reaction. The highest rate constants (10.45 × 10(-3) and 20.12 × 10(-3)) and degradation efficiencies at pH 2 and 7 were obtained at UV/O3 processes. In solution, after processes, benzene, phenol, acetophenone, o-hydroxybiphenyl, p-hydroxybiphenyl, benzoic acid, benzaldehyde, and biphenyl were identified.

We investigated the cloning, catalytic activity and anion inhibition of the beta-class carbonic anhydrases (CAs, EC 4.2.1.1) from the bacterial pathogen Legionella pneumophila. Two such enzymes, lpCA(1) and lpCA(2), were found in the genome of this pathogen. These enzymes were determined to be efficient catalysts for CO2 hydration, with k(cat) values in the range of (3.4-8.3) x 10(5) s(-1) and k(cat)/K-M values of (4.7-8.5) x 10(7) M-1 s(-1). A set of inorganic anions and small molecules was investigated to identify inhibitors of these enzymes. Perchlorate and tetrafluoroborate were not acting as inhibitors (K-I > 200 mM), whereas sulfate was a very weak inhibitor for both lpCA(1) and lpCA(2) (KI values of 77.9-96.5 mM). The most potent lpCA(1) inhibitors were cyanide, azide, hydrogen sulfide, diethyldithiocarbamate, sulfamate, sulfamide, phenylboronic acid and phenylarsonic acid, with K-I values ranging from 6 to 94 mu M. The most potent lpCA(2) inhibitors were diethyldithiocarbamate, sulfamide, sulfamate, phenylboronic acid and phenylarsonic acid, with K-I values ranging from 2 to 13 mu M. As these enzymes seem to be involved in regulation of phagosome pH during Legionella infection, inhibition of these targets may lead to antibacterial agents with a novel mechanism of action. (C) 2014 Elsevier Ltd. All rights reserved.

Hydrothermal reactions of sodium orthovanadate, copper(II) sulfate pentahydrate, phenylarsonic acid and an imine ligand yielded two compounds of the Cu(II)-imine/VxOy/RAsO3n− family. Under the conditions of this study the one-dimensional [Cu(phen)VO2(O3AsC6H5)(HO3AsC6H5)] (1) and the unique mixed-dimensionality structure of [Cu(bpy)VO2(O3AsC6H5)(HO3AsC6H5)][Cu(bpy)V2O4(O3AsC6H5)2] (2), which consists of a cluster and a one-dimensional chain, were produced. (phen = 1,10-phenanthroline, bpy = 2,2′-bipyridine)

Burkholderia pseudomallei is a Gram-negative saprophytic bacterium responsible of melioidosis, an endemic disease of tropical and sub-tropical regions of the world. A recombinant gamma-CA (Bps gamma CA) identified in the genome of this bacterium was cloned and purified. Its catalytic activity and anion inhibition profiles were investigated. The enzyme was an efficient catalyst for the CO2 hydration showing a km of 5.3 x 10(5) s(-1) and k(cat)/K-m of 2.5 x 10(7) M-1 x s(-1). The best Bps gamma CA inhibitors were sulfamide, sulfamic acid, phenylboronic acid and phenylarsonic acid, which showed K-I in the range of 49-83 mu M (these inhibitors showed millimolar inhibition constant against hCA II), followed by diethyldithiocarbamate, selenate, tellurate, perrhenate, selenocyanate, trithiocarbonate, tetraborato, pyrophosphate, stannate, carbonate, bicarbonate, azide, cyanide, thiocyanate and cyanate with K(I)s in the range of 0.55-9.1 mM. In our laboratories, work is in progress to resolve the X-ray crystal structures of Bps gamma CA, which may allow the development of small molecule inhibitors with desired properties for targeting and inhibiting specifically the bacterial over the human CAs, considering the fact that B. pseudomallei is involved in a serious bacterial disease. (C) 2016 Elsevier Ltd. All rights reserved.